Production of bituminous emulsion and liquid amine emulsifier therefor

ABSTRACT

A liquid amine compound which can be applied to various uses such as emulsification for bitumens since it has as high surface activity as those of solid amines and is more excellent in workability as compared with the solid amines, and an emulsifier for bitumens produced by using the amine compound. Furthermore, a process for producing an emulsifier a bituminous emulsion by reacting an aliphatic amine having at least one hydrocarbon group having not less than 8 carbon atoms with a carbonyl compound and adding an acid thereto to adjust the pH of the amine compound so as to be not more than 5, and a process for producing a bituminous emulsion composition by using the amine compound.

This application is the national phase under 35 U.S.C. §371 of prior PCTInternational Application No. PCT/JP96/02881 which has an Internationalfiling date of Oct. 3, 1996 which designated the United States ofAmerica, the entire contents of which are hereby incorporated byreference.

FIELD OF THE INVENTION

The present invention relates to a liquid amine compound which can beapplied to various uses such as emulsification for bitumens since it hasas high of a surface activity as solid amines and has a much betterworkability as compared with the solid amines, and to uses of the abovecompound thereby to emulsify the bitumens.

Further, the present invention provides a process for producing anemulsifier for bitumens, in which an acid is added to a liquid aminecompound obtained by reacting a specific aliphatic amine with a carbonylcompound to adjust the pH so as to be not more than 5.

DESCRIPTION OF THE RELATED ART

In cationic surfactants used as emulsifiers for bitumens, hydrochloridesof aliphatic amines have so far been used in the form of an aqueoussolution, and those having linear alkyl groups having 12 to 22 carbonatoms have been known as industrially useful ones. Since these aminecompounds have long linear alkyl groups, they are solid or pasty at roomtemperatures and difficult to handle when using them.

Efforts for liquefying these amine compounds have so far been made butthey have involved the following problems.

For example, a method for oxyalkylating alkylamines andalkylpropylenediamines, described in U.S. Pat. No. 2,930,701 and FrenchPatent 1,462,981, and a method for methylating secondary nitrogen,disclosed in U.S. Pat. No. 4,561,900, sacrifice considerably theinterface active characteristics. That is, in various applications, moreaddition amounts are required as compared with those of raw materialsolid amines, or in the case of making use of them for a purpose ofpreparing emulsions, more greater mechanical energy is needed.

Further, it can be considered to dilute them into liquids by organicsolvents. In this case, however, it is difficult to raise the amineconcentration to 60% or higher even with the use of lower alcoholshaving the largest dissolution power, and therefore the considerablylarge amounts of the organic solvents have to be blended. In this case,it is apparent that the evaporation of the organic solvents exerts anadverse effect on the environment, and the adverse effects of theorganic solvents may be exerted on the performances according to theuse.

Further, it is described in U.S. Pat. No. 4,701,484 to use the reactionproducts of organic amine compounds primarily with unsaturated aldehydes(acrolein and the like) as aldehyde compounds as an anti-strippingadditive (an agent for increasing an adhesion between aggregates andasphalt in a hot mix composition) for heated asphalt. However, the abovereaction products are nothing but disclosed as the anti-stripping agentfor heated asphalt, and descriptions in terms of emulsification ofbitumens are not found at all.

SUMMARY OF THE INVENTION

Intensive investigations made by the present inventors in order to solvethe problems described above have resulted in finding that the reactionof an aliphatic amine having at least one hydrocarbon group having notless than 8 carbon atoms with a carbonyl compound can liquefy the aminecompound without damaging the interface activity and that this liquidamine compound is excellent as a component for an emulsifier forbitumens, and thus coming to complete the present invention.

That is, the present invention relates to use of a liquid amine compoundprepared by reacting an aliphatic amine having at least one hydrocarbongroup having not less than 8 carbon atoms with a carbonyl compound foran emulsifier of bitumens.

Further, the present invention relates to use of a liquid aminecomposition prepared by adding at least one compound selected from thegroup consisting of (a) organic acids, (b) alcohols and (c) phenols to aliquid amine compound prepared by reacting the aliphatic amine having atleast one hydrocarbon group having not less than 8 carbon atoms with acarbonyl compound for an emulsifier of bitumens.

The present invention relates to a liquid amine compound for emulsifyingbitumens which is prepared by reacting an aliphatic amine having atleast one hydrocarbon group having not less than 8 carbon atoms with acarbonyl compound.

Further, the present invention provides use of the liquid amine compoundfor an emulsifier of bitumens in water, and an emulsion compositioncomprising the liquid amine compound described above, a bitumen andwater.

That is, the present invention relates to a process for producing anemulsifier for producing a bituminous emulsion, wherein an acid is addedto the liquid amine compound for an emulsifier of bitumens to adjust thepH of the aqueous solution so as to be not more than 5.

Further, the present invention relates to a process for producing abituminous emulsion composition, in which to a mixture comprising 50 to80 wt % of bitumen and 50 to 20 wt % of water is added 0.05 to 10.0 wt %per the mixture of a liquid amine compound, which amine compound hasbeen prepared by reacting an aliphatic amine having at least onehydrocarbon group having not less than 8 of carbon atoms and a carbonylcompound, and then an acid is added thereto to adjust the pH of theobtainable emulsion so as to be not more than 5 for controlling theequivalent ratio of the composition.

Also, the present invention relates to a liquid amine mixture comprisingan aliphatic poly-amine having at least one hydrocarbon group having notless than 8 carbon atoms and a carbonyl compound.

Further, the present invention relates to a liquid amine compoundprepared by reacting an aliphatic amine obtained by mixing an aliphaticmono-amine having at least one hydrocarbon group having not less than 8carbon atoms with an aliphatic poly-amine having at least onehydrocarbon group having not less than 8 carbon atoms with a carbonylcompound.

Further, the present invention relates to a liquid amine compositionprepared by adding at least one compound selected from the groupconsisting of (a) organic acids, (b) alcohols and (c) phenols to theprescribed amine compound.

DETAILED DESCRIPTION OF THE INVENTION

The liquid amine compound of the present invention, a production processof an emulsifier for producing a bituminous emulsion using the liquidamine compound, and a production process for a bituminous emulsion usingthe emulsifier will be described below in detail.

In producing the liquid amine compound of the present invention, analiphatic amine (hereinafter referred to as the raw material amine)having at least one hydrocarbon group having not less than 8 carbonatoms is reacted with a carbonyl compound in the following conditions.

The reaction temperature is preferred to be in the range from themelting point of the raw material amine to about 200° C., morepreferably 50 to 150° C. High temperatures exceeding 200° C. are notpreferred since the raw material amine is deteriorated. On the otherhand, at temperatures being lower than the melting point of the rawmaterial amine, the raw material amine is in the state of solid so thatthe uniform reaction is not obtained.

The carbonyl compound used in the present invention can be used in theform of an aqueous solution. When the carbonyl compound is liquid, itcan be used as it is. In the present invention, the reaction can becarried out by a method in which these liquids are dropwise added littleby little to the molten raw material amine maintained at prescribedtemperatures. This is because the reaction is a exothermic reaction,therefore, it is needed to facilitate temperature control. Accordingly,it is advantageous to add dropwise either of the raw material amine andthe carbonyl compound over a some period of time, for example,preferably over a period of 0.1 to 5 hours. The raw material amine maybe added dropwise to the carbonyl compound. Further, the raw materialamine which has been molten by heating and the carbonyl compound can befed at the same time into a reactor maintained at prescribedtemperatures to react them continuously. In such a continuous process,the feed rates of the raw materials can be controlled so that theretention time of the reaction is 0.1 to 5 hours in order to completethe reaction.

In a batch system reaction, the reaction liquid is aged for furtherabout 1 to 5 hours after finishing dropwise adding in order to completethe reaction. The aging temperatures may be the same as or higher thanthe temperature in dropwise adding.

Further, it is preferred to carry out a dehydration after aging in orderto remove out water remaining in the reaction mixture. This is becausewhen water remains in the product, the water is gradually separatedduring storage, and the product may unfavorably become heterogeneous.The dehydration may be carried out at temperatures elevated up to 100°C. or higher or may be carried out at temperatures of 100° C. or lowerunder reduced pressure. In the continuous process, the dehydration canbe achieved by feeding the reaction mixture into a distillation columnmaintained at such temperatures and pressure. The product can bemaintained homogeneously even when water remains in some cases accordingto the kind of the raw material amine, and therefore the dehydration isnot needed.

A charge mole ratio of the carbonyl compound to the amine is preferably0.1 to 10 times mole, more preferably 1.0 to 2.0 times mole. The moleratio of less than 0.1 time mole reduces a fluidity-providing effect tothe amines, which is the effect of the present invention. Meanwhile, thecharge mole ratio exceeding 10 times mole does not further increase theeffect.

The carbonyl compound used in the present invention includes aldehydeshaving 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms and ketoneshaving 3 to 8 carbon atoms.

As examples of the aldehyde having 1 to 18 carbon atoms, aliphaticaldehydes such as formaldehyde, acetaldehyde, glyoxal, propanal,n-butylaldehyde, isobutylaldehyde, crotonaldehyde, pentanal, hexanal,ethylbutylaldehyde, heptanal, octanal, 2-ethylhexylaldehyde,pelargonaldehyde, caprinic aldehyde, undecylaldehyde, lauraldehyde,tridecylaldehyde, myristaldehyde, pentadecylaldehyde, palmitaldehyde,margaraldehyde and stearic aldehyde; and heterocyclic aldehydes such asfurfural can be cited. Further, paraformaldehyde can also be used as araw material for formaldehyde. Among them, aldehydes having 1 to 10carbon atoms, preferably 1 to 8 carbon atoms are preferred.

As examples of the ketone having 3 to 8 carbon atoms, aliphatic ketonessuch as acetone, methyl ethyl ketone, ethyl ketone, 1-pentanone, methylpropyl ketone, 2-hexanone, 3-hexanone, methyl isobutyl ketone,1-heptanone, methylpentanone and octanone can be cited.

The aliphatic amine having at least one hydrocarbon group having 8 ormore carbon atoms, which is the raw material amine used in the presentinvention includes the aliphatic amines represented by the followingformula. Among them, the aliphatic amines having at least one linearhydrocarbon group having 8 to 22 carbon atoms are preferred.

    R.sub.1 R.sub.2 N (ANH).sub.p H

(wherein, R₁ represents a linear hydrocarbon group having 8 to 22 carbonatoms; R₂ represents H or a linear hydrocarbon group having 8 to 22carbon atoms; A represents an ethylene group or a propylene group; and pis a number of 0 to 4).

Specifically, the above aliphatic amines include mono-amines such asdecylamine, laurylamine, myristylamine, cetylamine, stearylamine, tallowamine and hydrogenated tallow amine; and diamines obtained by reactingthem with acrylonitrile and hydrogenating thereof, for examples,N-aminopropyldecylamine, N-aminopropyllaurylamine,N-aminopropylmyristylamine, N-aminopropylcetylamine,N-aminopropylstearylamine, and N-aminopropyl tallow amine. Further,triamines and tetraamines into which amino nitrogens are introduced byrepeating the same process can be given as the examples. They include,for example, triamines such as N-decyldipropylenetriamine,N-lauryldipropylenetriamine, N-myristyldipropylenetriamine,N-cetyldipropylenetriamine, N-stearyl-dipropylenetriamine and N-tallowalkyldipropylenetriamine; and tetraamines such asN-lauryltripropylenetetraamine, N-myristyltripropylenetetraamine,N-cetyltripropylenetetraamine, N-stearyltripropylenetetraamine andN-tallow alkyltripropylenetetraamine. They may be subjected tohydrogenation treatment by conventional methods after reacting with thecarbonyl compound. In the present invention, among them, tallow amines,tallow poly-amines, hydrogenated tallow amines, and hydrogenated tallowpoly-amines which are derived from beef tallow are preferred.

Particularly preferred aliphatic amine is at least one selected from thealiphatic mono-amine and the aliphatic poly-amine, a mixture of thealiphatic mono-amines and the aliphatic poly-amines, or at least oneselected from the group consisting of tallow mono-amine, tallowpoly-amine, hydrogenated tallow mono-amine, and hydrogenated tallowpoly-amine which are derived from tallow, especially from beef tallow.

Further, the aliphatic amines represented by the formula described abovein which R₁ or R₂ has preferably 10 to 22 carbon atoms, more preferably12 to 22 carbon atoms, most preferably 16 to 18 carbon atoms.

In the present invention, the aliphatic amines described above can beused alone or in a mixture of two or more kinds thereof. When they areused in a mixture of two or more kinds thereof, the mixture preferablycomprises the mono-amine and the poly-amine in terms of an emulsifyingability. When the mixture comprising the mono-amine and the poly-amineis used, a ratio of the mono-amine to the poly-amine is 10:90 to 60:40.

In the present invention, the reaction of the aliphatic amine having atleast one hydrocarbon group having not less than 8 carbon atoms with thecarbonyl compound is considered to be a nucleophilic addition reactionof amine nitrogen to a carbonyl carbon and a dehydration reactionfollowing it.

The chemical structure of a product obtained by reacting a formaldehydewith the amine is considered to mainly comprise a dimer and a trimerwhich dimer and trimer are obtained by bonding intermolecularlynitrogens of the amine molecules via methylene bonds.

For example, in the case of a reaction of N-aminopropyl tallowalkylamine with formaldehyde, the following values were obtained as theanalytical values of the product obtained in the reaction in which thecharge mole ratio of formaldehyde to amine has been 1.5.

                  TABLE 1                                                         ______________________________________                                                        Raw material                                                    amine Product                                                               ______________________________________                                        Total amine value 342       168                                                 Primary amine value 187 16                                                    Secondary amine value 147 11                                                  Tertiary amine value 8 141                                                  ______________________________________                                    

According to the above, bonding among amine nitrogens via methylenebonds reduces primary and secondary amines and markedly increasestertiary amines. It has been found that the amine molecules aremethylene-bridged to be polymerized. Nitrogen turned into a Schiff baseby the reaction of a primary amino group with aldehyde andmethylene-bridged nitrogen have a very low basicity, and this results ina reduction in the total amine value of the product. The followingvalues were obtained as the analytical values of the product obtained bythe reaction of n-butylaldehyde with N-aminopropyl tallow alkylamine inan amount of 1.5 time mole per the amine.

                  TABLE 2                                                         ______________________________________                                                        Product                                                       ______________________________________                                        Total amine value 295                                                           Primary amine value 217                                                       Secondary amine value 68                                                      Tertiary amine value 10                                                     ______________________________________                                    

In this case, the molecular weight was observed to merely increase onlyby a portion obtained by a condensation of n-butylaldehyde. The tertiaryamine increased slightly, and dimerization and trimerization caused bycondensation of the molecules scarcely took place. The resulting productwas liquid.

Turbidity of a product is generated in some cases during storage of theproduct over a long period of time. In order to prevent this, at leastone compound selected from the group consisting of (a) organic acids,(b) alcohols and (c) phenols in an amount of 1 to 20 wt % can be addedto the aliphatic amine to be used in the reaction during or afterproducing the liquid amine. When the organic acids (a) and the phenols(c) are used, they are added preferably to a reaction mixture whileproducing the liquid amine, and in the case of the alcohols (b), theyare added preferably to a reaction mixture after producing the liquidamine.

Preferable examples of the organic acids (a) include aliphaticcarboxylic acids having 1 to 22 carbon atoms and are liquid at roomtemperatures, for example, formic acid, acetic acid, propionic acid,butyric acid, isobutyric acid, pentanoic acid, trimethylacetic acid,2-methylbutanoic acid, 3-methylbutanoic acid, caproic acid, heptanoicacid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, isostearicacid, oleic acid, linoleic acid and linolenic acid. The organic acidshaving carbon atoms exceeding 22 are not preferred since they are solidat room temperatures and can be a factor of turbidity in some cases.

Preferable examples of the alcohols (b) include monohydric alcohols suchas methyl alcohol, ethyl alcohol, isopropyl alcohol and oleyl alcohol;and polyhydric alcohols such as ethylene glycol, propylene glycol,glycerol, polyglycerol, diethylene glycol, polyethylene glycol andpolypropylene glycol. Among them, polyhydric alcohols are preferred.

Preferable examples of the phenols (c) include phenol; alkylphenols suchas cresol, 3,5-xylenol, nonylphenol, p-tert-butylphenol andisopropenylphenol; phenylphenol; resorcinol; catechol; hydroquinone;floroglucin, hydrolyzable tannins such as cashew nut husk liquid,gallnut, gall, smack, tara, varonia, myrobalan, oak (Kashiwa),divi-divi, algarobilla, laishtan and cascalote; condensed tannins suchas gamvia, quebracho, mimosa, acacia, mangrove, hemlock, spruce,bilumaccachi, oak bark and persimmon tannin; degiputo, Chinese tannin,Turkish tannin, hamameli tannin, quebric acid tannin, ellagic acidtannin and refined tannic acids thereof; polyhydric phenols such asliqnin; and bisphenols such as bisphenol A, bisphenol F, bisphenol C andbisphenol E. Among them, polyhydric phenols are preferred.

According to the present invention, a cationic surfactant derived fromthe liquid amine compound and a bituminous emulsion compositioncontaining the cationic surfactant as an essential component can beproduced as well.

Turbidity present in the liquid amine compound obtained by reacting theamine compound with the carbonyl compound does not exert an adverseeffect on an emulsifying ability in using the liquid amine compound as acationic surfactant but causes the problem of bad appearance of theproduct in some cases. Pursuit of the cause of the turbidity hasresulted in finding that non-amine components contained in the rawmaterial amine are strongly related to it. In particular, among thenon-amine components, amides having high solidifying points are liableto cause formation of the turbidity. It has been found that the liquidamine compound containing reduced turbidity matters or having noturbidity can be obtained by using the raw material amine containingless non-amine components.

The non-amine components are impurities contained in the amine compound,and the components which are not adsorbed on cation exchange resins areshown by weight percentage based on the weight of the sample.

Non-amine components derived from tallow fatty acids include amides suchas myristic acid amide, palmitic acid amide, stearic acid amide,dimyristic acid amide, dipalmitic acid amide and distearic acid amide;and nitriles such as myristnitrile, palmitnitrile, and stearonitrile.Further, it is considered that a polymer of acrylonitrile andhydrocarbons used when the poly-amines are derived from the mono-aminesare contained.

Results obtained by testing the effect of the turbidity caused by thenon-amine components are shown in Table 3. The non-amine components aredetermined in the following manner:

Determination of non-amine component:

5×10⁻³ g equivalent of amine sample was dissolved in 200 ml ofisopropanol and regenerated with a hydrochloric acid aqueous solution.Then, the solution was put into a 500 ml separating funnel together with50 ml of cation exchange resins (Dowex 50 W×4, 50 to 100 mesh) which hasbeen washed by isopropanol. The solution was shaken by means of asuitable shaking apparatus for about one hour to adsorb the aminecomponents on the resins. After finishing shaking, the resin wasfiltered off, and isopropanol was distilled off from the filtrate. Thenon-adsorbed matters were weighed to determine a weight percentagethereof based on the weight of the sample.

                  TABLE 3                                                         ______________________________________                                        Influence of Non-amine component to Turbidity                                   Amount of Turbid                                                              substance vol % (based                                                        on liquid amine)                                                              Kind of aldehydes (mole                                                       ratio) Propion- Isobutyl- Isobutyl-                                           Raw material aldehyde aldehyde aldehyde (1.5)                                 amine (non-amine (1.2) (1.5) reactant +                                       component, wt %) reactant reactant 2EH acid 5 wt %*                         ______________________________________                                        Hydrogenated tallow                                                             monoamine                                                                     (0.7) 1.6 2.0 0.0                                                             (0.4) 5.0 8.0 0.8                                                             Tallow diamine                                                                (2.8) 1.4 1.4 0.0                                                             (6.8) 5.8 4.2 0.6                                                             Tallow triamine                                                               (4.7) 2.5 1.2 0.0                                                             (9.6) 4.0 4.8 0.4                                                           ______________________________________                                         *2-EH: 2ethylhexanoic acid                                               

As shown by Table 3, it can be found that the turbidity of the productscan be reduced by using the raw material amines containing lessnon-amine components and that the turbidity can be overcome by adding asmall amount of a branched acid (2-ethylhexanoic acid). In the presentinvention, the non-amine components contained in the aliphaticmono-amines reside preferably in an amount of not more than 1 wt %; thenon-amine components contained in the aliphatic diamines residepreferably in an amount of not more than 5 wt %; and the non-aminecomponents contained in the aliphatic triamines reside preferably in anamount of not more than 10 wt %. The non-amine components contained inthe aliphatic tetramine or higher (amines in which p is 3 or more in theformula defined in above) reside preferably in the amount of not morethan 10 wt %.

The liquid amine compound of the present invention is preferably used asa component for an asphalt emulsifier for road paving, roofing andwater-proofing for revetment, and a component for anti-solidificationagents for fertilizers and collectors for floatations.

When the liquid amine compound of the present invention is used for anemulsifier for bitumens, the liquid amine compound can be used as wellin a mixture with other liquid amine compounds. The other liquid aminecompounds include conventional liquid amine compounds. Among them,liquid poly-amine compounds are preferred. Further, the liquidpoly-amine compounds include preferably poly-amine compounds having atleast one unsaturated hydrocarbon group having 12 to 22 carbon atoms,liquid amine compounds derived from tall oil, and liquid poly-aminecompounds obtained by adding alkylene oxide to aliphatic poly-amineshaving at least one straight or branched hydrocarbon group having 12 to22 carbon atoms. A blend ratio of the liquid amine compound of thepresent invention to the other liquid amine compounds falls in a rangeof 10 to 60 wt %, preferably 30 to 50 wt % in terms of a content of theliquid amine compound according to the present invention.

Next, the bituminous emulsion composition of the present invention and aproduction process therefor will be explained.

The liquid amine compound of the present invention can be used as acationic surfactant for emulsifying bitumens in the forms of acid saltsof hydrochloric acid, perchloric acid, formic acid, acetic acid,monochloroacetic acid, nitric acid, sulfamic acid and methylsulfuricacid, or in the forms of quaternary ammonium salts using quaternizingagents such as dimethylsulfuric acid and methyl chloride. In this case,other surfactants can be used in combination.

The liquid amine compound of the present invention is decomposed into anacid salt of the raw material aliphatic amine and the carbonyl compoundby deriving the liquid amine compound into the acid salt withhydrochloric acid or acetic acid and preparing an acid salt aqueoussolution thereof (emulsifier). This decomposition ratio is variedaccording to an equivalent ratio of the acid, a concentration of theliquid amine compound contained in the aqueous solution, and thetemperatures. The higher the decomposition ratio is, the better theemulsifying ability for the bituminous emulsion is, and the more stableemulsion is obtained.

Preferably, at least one compound selected from the group consisting of(a) organic acids, (b) alcohols and (c) phenols is added to the liquidamine compound, and an acid is further added thereto to adjust the pH ofthe aqueous solution so as to be not more than 5, whereby the emulsifieris obtained. Also preferably, a mixture comprising 50 to 80 wt % of abitumen and 50 to 20 wt % of water to which the liquid amine compounddescribed above is added in an amount of 0.05 to 10.0 wt % per themixture, and an acid is added to adjust the pH of the resulting emulsionso as to be not more than 5, whereby the bituminous emulsion compositionis produced.

More preferably, a mixture comprising 50 to 80 wt % of a bitumen and 50to 20 wt % of water to which the liquid amine compound described aboveis added in an amount of 0.05 to 10.0 wt % per the mixture. Then, atleast one compound selected from the group consisting of the organicacid (a), the alcohols (b) and the phenols (c) is added to the liquidamine compound, and an acid is added there to adjust the pH of theresulting emulsion so as to be not more than 5, whereby the bituminousemulsion composition is produced.

According to the above, the liquid amine compound of the presentinvention is preferably used after adjusting the pH of the derived acidsalt aqueous solution so as to be not more than 5, preferably 0.1 to 4,more preferably 1.0 to 2.5. In this condition, the decomposition ratiois increased as compared with a condition where the pH exceeds 5, andtherefore the higher emulsifying ability can be obtained.

The decomposition ratio at 25° C. in the case where the concentration ofthe hydrochloride is 0.7 wt % and the pH is adjusted to be 2.0 falls ina range of 60 to 98 wt %. The decomposition ratio can be obtained bydetermining the carbonyl compound produced in the aqueous solution.

The bituminous emulsion is a bituminous water-base emulsion obtained byemulsifying a bitumen with a emulsifier (surfactant).

The bitumen used in the present invention includes petroleum straightasphalt, semi-blown asphalt, cut-back asphalt, natural asphalt,petroleum tar, pitch, solvent-deasphalting asphalt, heavy oil, and amixture of two or more kinds thereof.

Further, there can be used as well reformed asphalts blended withnatural rubber, synthetic rubber such as styrene-butadiene copolymer andchloroprene copolymer, polymers such as polyethylene and ethylene-vinylacetate copolymer, petroleum resins, and thermoplastic resins.

Surfactants to be used in combination in the present invention includethe following ones.

Anionic surfactants include the following ones:

(I) formaldehyde condensation products of aromatic compounds such asnaphthalene, alkylnaphthalene, alkylphenol and alkylbenzene withsulfonic acid or salts thereof; an average condensation degree offormaldehyde is preferably 1.2 to 100;

(II) formaldehyde condensation products of liqnosulfonic acid,liqnosulfonic acid salts, derivatives thereof, and aromatic compoundssuch as liqnosulfonic acid and naphthalene, and alkylnaphthalene withsulfonic acid, and salts of the formaldehyde condensation products; anaverage condensation degree of formaldehyde is preferably 1.2 to 50;

(III) polystyrenesulfonic acid or salts thereof, and copolymers ofstyrenesulfonic acid and other copolymerizable monomers, and saltsthereof; the molecular weights are 500 to 500,000;

(IV) dicylopentadienesulfonic acid polymer or salts thereof; themolecular weights of the polymers are preferably 500 to 500,000;

(V) polyacrylic acid or salts thereof, and copolymers of acrylic acidand other copolymerizable monomers, and salts thereof; the molecularweights are preferably 500 to 500,000;

(VI) maleate of liquid polybutadiene; a molecular weight of the liquidpolybutadiene is preferably 500 to 200,000;

(VII) copolymers of anhydrous maleic acid and/or anhydrous itaconic acidwith other copolymerizable monomers; the molecular weights arepreferably 500 to 500,000;

(VIII) the following anionic surfactants each having one or twohydrophilic groups in a molecule; (a) sulfuric acid ester salt ofalcohol having 4 to 18 carbon atoms;

(b) alkane, alkene and/or alkylarylsulfonic acid having 4 to 18 carbonatoms, or salts thereof;

(c) sulfates or phosphates of alkyleneoxide adducts of compounds havingat least one active hydrogen in a molecule, and salts thereof;

(d) sulfosuccinic acid salts which are esters of saturated orunsaturated fatty acids having 4 to 22 carbon atoms;

(e) alkyldiphenyl ether disulfonic acid or salts thereof; the alkylgroup has 8 to 18 carbon atoms;

(f) rosinic acid or salts thereof; a mixed acid of rosinic acid and talloil which is a mixed acid of higher fatty acids, and salts thereof;

(g) alkane or alkenefatty acids having 4 to 18 carbon atoms, and saltsthereof;

(h) α-sulfofatty acid ester salt represented by the following formula:##STR1## (wherein R₃ represents an alkyl group or alkenyl group having 6to 22 carbon atoms; R₄ represents an alkyl group having 1 to 22 carbonatoms; M represents a monovalent or divalent metal atom, NH₄ or organicamine; and n is 1 or 2).

In the compounds (I) to (VIII), the salts include lower amines such asammonium, monoethanolamine, diethanolamine, triethanolamine andtriethylamine; and alkaline metals or alkaline earth metals such assodium, potassium, magnesium and calcium.

The cationic surfactants include alkylamine salts, alkanolamine salts,quaternary ammonium salts, amine oxides and polyethylenepolyamines, andadducts of ethylene oxide and propylene oxide are included as well. Inthe case of the cationic surfactants which are not quaternary salts,they are used in the respective forms of acid salts of hydrochloricacid, acetic acid, nitric acid, sulfamic acid, and methylsulfuric acid.

The nonionic surfactants include polyethylene glycol type surfactantssuch as higher alcohol-ethylene oxide adducts, alkylenephenol-ethyleneoxide adducts, fatty acid-ethylene oxide adducts, polyhydricalcohol-fatty acid ester-ethylene oxide adducts, higheralkylamine-ethylene oxide adducts, fatty acid amide-ethylene oxideadducts, oil or fat-ethylene oxide adducts and polypropyleneglycol-ethylene oxide adducts; and polyhydric alcohol type surfactantssuch as fatty acid esters of glycerol, fatty acid esters ofpentaerythritol, fatty acid esters of sorbitol and sorbitan, fatty acidesters of sucrose, polyalkylene glycol dialkyl esters, alkyl ethers ofpolyhydric alcohols, reaction products of alkylene oxide adducts andepoxy compounds, and fatty acid amides of alkanolamines.

The amphoteric surfactants include carboxylic acid salts of amino acidtype and betaine type, sulfuric acid esters, sulfonic acid salts andphosphoric acid esters.

Further, water soluble inorganic salts such as ammonium chloride,calcium chloride, aluminum chloride, and iron chloride can be used incombination.

In addition to the above, polyhydric alcohols, polymer stabilizers andorganic acids can be comprised as well. Any alcohols can be used as thepolyhydric alcohols as long as they have at least 2 hydroxyl groups in amolecule and are soluble in water, for example, glycerol, polyglycerol,ethylene glycol, diethylene glycol, polyethylene glycol, propyleneglycol, and monosaccharides and polysaccharides such as sorbitol andglucose.

Various water soluble polymers having molecular weights of 10,000 ormore shown in Table 4 can be comprised as the polymer stabilizers.

Organic acids which are solid at room temperatures are preferredinclude, for example, aliphatic monohydric carboxylic acids such asundecylic acid, lauric acid, myristic acid, palmitic acid, stearic acid,hydroxystearic acid, arachidonic acid, behenic acid and erucic acid;aliphatic dihydric carboxylic acids such as oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid and dimer acid; aromatic monohydriccarboxylic acids such as benzoic acid, salicylic acid, p-hydroxybenzoicacid, toluic acid, aminobenzoic acid, sulfobenzoic acid, gallic acid,phenylacetic acid, mandelic acid, and phenylacrylic acid, phthalic acid,trimellitic acid, pyromellitic acid, and tannic acid.

                                      TABLE 4                                     __________________________________________________________________________    Polymer stabilizer                                                            __________________________________________________________________________    Water soluble synthetic polymer                                                                  Water soluble natural polymer                                polyvinyl alcohol, sodium polyacrylic acid, Arabic gum, tragacanth gum,                        karaya gum, guar                                             polyacrylamide, polyvinyl pyrrolidone, gum, tara gum, locust bean gum,                         tamarind gum,                                                polyvinyl methylether, polyvinyl sulfone, sodium alginate, alginic acid       maleic acid copolymer, polyethylene oxide, propyleneglycolester,                               carageenan,                                                  polydiallylamine, polyethyleneimine furcellaran, agar, high-methoxy                            pectin, low-                                                 Water soluble cellulose derivative methoxy pectin, chitin, chitosan                             carboxymethyl cellulose, methyl cellulose, Fermentable                        polysaccharide                                              methylhydroxypropyl cellulose,                                                hydroxyethyl cellulose, hydroxypropyl xanthane gum, pulluran, cardran,                         dextran                                                      cellulose, other mixed ethers, sodium                                         cellulose sulfuric acid ester                                                 Protein Other                                                                 milk casein, sodium casein, gelatin, chondroitin sulfuric acid,                                hyaluronic acid                                              albumin, soy been casein                                                    __________________________________________________________________________

A combined use ratio of the liquid amine compound of the presentinvention to the other surfactants is preferably 10 to 500 wt % of theother surfactants (including polyhydric alcohols and the polymerstabilizers) based on the liquid amine compound.

In the bituminous emulsion composition of the present invention, ablending ratio of the bitumen to water is preferably 50 to 80 wt % ofthe bitumen to 50 to 20 wt % of water. An addition amount of the liquidamine compound or liquid amine composition of the present invention issuitably 0.05 to 10.0 wt %, preferably 0.1 to 3.0 wt % based on the sumof the bitumen and water.

The bituminous emulsion composition can be prepared by preparing anaqueous solution of the surfactant described above and feeding theaqueous solution and an asphalt molten by heating into an emulsifyingapparatus at the same time. An aqueous solution of the cationicsurfactant of the present invention can be prepared by turning theliquid amine compound of the present invention into the form ofhydrochloride or acetate.

The method for preparing the bituminous emulsion composition includes amethod in which the liquid amine compound or composition of the presentinvention, water, an acid such as hydrochloric acid and acetic acid ofan amount sufficient to adjust the pH of the aqueous solution so as tobe not more than 5, preferably 1 to 4, and particularly preferably 1.0to 2.5 in blending later, and asphalt molten by heating are fed into anemulsifying apparatus at the same time to prepare the bituminousemulsion composition (first method), a method in which an aqueoussolution of the liquid amine compound or composition of the presentinvention is prepared, and the aqueous solution, an acid such ashydrochloric acid and acetic acid of an amount sufficient to adjust thepH of the aqueous solution so as to be not more than 5, preferably 1 to4, and particularly preferably 1.0 to 2.5, and an asphalt molten byheating are fed into an emulsifying apparatus at the same time toprepare the bituminous emulsion composition (second method), and amethod in which an aqueous solution of the liquid amine compound orliquid amine composition of the present invention, which is turned intothe form of hydrochloride or acetate, wherein the pH is adjusted to benot more than 5, preferably 1 to 4, and particularly preferably 1.0 to2.5, and an asphalt molten by heating are fed into an emulsifyingapparatus at the same time to prepare the bituminous emulsioncomposition (third method). These aqueous solutions are used by heatingat 25 to 98° C., preferably 40 to 70° C. The temperatures falling out ofthis range increase an asphalt particle diameter of the resultingemulsion and exert an adverse effect on the storage stability in somecases.

In general, temperatures for heating the asphalt are varied according tothe penetration, and the asphalt having a smaller penetration has to beheated at higher temperatures. For example, the asphalt having apenetration of 80 to 100 can be used by heating at 130 to 150° C.

In the three methods described above, the respective components can bepreblended before feeding into an emulsifying apparatus.

The emulsifying apparatus capable of being used in the present inventionincludes emulsifying apparatus and dispersing machines such as ahomomixer, a homogenizer, a line mixer, a colloid mill, a sand mill, amilder, and a motionless mixer.

A shear rate in emulsifying is preferably 5,000 to 200,000 s⁻¹, morepreferably 20,000 to 80,000 s⁻¹. The lower shear rate provides theemulsion composition having a larger asphalt particle diameter andcauses a problem on a storage stability. Meanwhile, the shear rate whichis increased too much can not provide the fine particle diameter andmerely increases an energy consumption.

EXAMPLES

The present invention will now be explained in detail with reference tothe examples shown below but the present invention is not be limited bythese examples.

Example 1

200 g of tallow alkylpropylenediamine (total amine value: 342 mg KOH/g)was weighed to feed into a 1 liter four neck flask and heated to 65° C.99.0 g of 37% formalin aqueous solution was dropwise added over a periodof 3 hours. After aging at the same temperature for one hour,dehydration was carried out. The final condition of the dehydration was75° C./50 mm Hg. The resulting reaction product showed fluidity at roomtemperatures. An analysis thereof resulted in showing that the totalamine value was 165 mg KOH/g and the solidification temperature was 8°C. The solidification temperature was determined by evaluating thefluidity by every 1° C. in accordance with JIS K 2269. The infraredabsorption spectra of the tallow alkylpropylenediamine and the resultingreaction product are shown in FIG. 1, the H-NMR spectra of the tallowalkylpropylenediamine and the resulting reaction product are shown inFIG. 2; and the analytical results of the resulting reaction productdetermined by GPC are shown in FIG. 3. The measuring conditions of GPCare as follows:

[Measuring conditions of GPC]

Column filler: styrene-divinylbenzene copolymer G2000 HXL+G1000 HXL(mfd. by Toso Co., Ltd.) (inner diameter: 7.8 mm and length: 30 cm incommon)

Eluate: tetrahydrofuran

Detecting element: RI

Example 2

The amine compound obtained in Example 1 was subjected to hydrogenationtreatment. The hydrogenation was carried out with a Raney nickelcatalyst at a temperature of 130° C., 15 kg and for 2 hours. An analysisof the resulting product showed that the total amine value was 320.4 mgKOH/g and the solidification temperature was 9° C.

Example 3

200 g of tallow alkylpropylenediamine (total amine value: 342 mg KOH/g)was weighed to feed into a 1 liter four neck flask and heated to 65° C.49.4 g of 37% formalin aqueous solution was dropwise added over a periodof 2 hours. After aging at the same temperature for one hour,dehydration was carried out. The final condition of the dehydration was75° C./50 mm Hg. The resulting reaction product showed fluidity at roomtemperatures, and an analysis thereof resulted in showing that the totalamine value was 190.2 mg KOH/g and the solidification temperature was10° C. The analytical results of the resulting reaction productdetermined by GPC are shown in FIG. 4.

Example 4

320 g of tallow alkyldipropylenetriamine (total amine value: 426 mgKOH/g) was weighed to feed into a 1 liter four neck flask and heated to85° C. 98.5 g of 37% formalin aqueous solution was dropwise added over aperiod of 2 hours. After aging at the same temperature for one hour,dehydration was carried out. The final condition of the dehydration was85° C./50 mm Hg. The resulting reaction product showed fluidity at roomtemperatures, and an analysis thereof resulted in showing that the totalamine value was 311.0 mg KOH/g and the solidification temperature was 9°C.

Example 5

200 g of tallow alkyltripropylenetetraamine (total amine value: 485 mgKOH/g) was weighed into a 1 liter four neck flask and heated to 60° C.87.6 g of 37% formalin aqueous solution was dropwise added over a periodof 2 hours. After aging at the same temperature for 2 hours, dehydrationwas carried out. The final condition of the dehydration was 75° C./40 mmHg. The resulting reaction product showed fluidity at room temperatures,and an analysis thereof resulted in showing that the total amine valuewas 293.6 mg KOH/g and the solidification temperature was 5° C.

Example 6

350 g of tallow alkyltripropylenetetramine (total amine value: 485 mgKOH/g) was weighed to feed into a 1 liter four neck flask and heated to60° C. 42.9 g of 37% formalin aqueous solution was dropwise added over aperiod of 2 hours. After aging at the same temperature for 2 hours,dehydration was carried out. The final condition of the dehydration was75° C./50 mm Hg. The resulting reaction product showed fluidity at roomtemperatures, and an analysis thereof resulted in showing that the totalamine value was 353.6 mg KOH/g and the solidification temperature was 7°C.

Example 7

400 g of tallow alkyltripropylenetetraamine (total amine value: 485 mgKOH/g) was weighed to feed into a 1 liter four neck flask and heated to65° C. 71.6 g of 80% acetaldehyde aqueous solution was dropwise addedover a period of 2 hours. After aging at the same temperature for 2hours, dehydration was carried out. The final condition of thedehydration was 80° C./50 mm Hg. The resulting reaction product showedfluidity at room temperatures, and an analysis thereof resulted inshowing that the total amine value was 343.6 mg KOH/g and thesolidification temperature was 6° C.

Example 8

200 g of stearylethylenediamine (total amine value: 342 mg KOH/g) wasweighed to feed into a 1 liter four neck flask and heated to 80° C. 90.6g of n-butylaldehyde was dropwise added over a period of 2 hours. Afteraging at the same temperature for 2 hours, dehydration was carried out.The final condition of the dehydration was 80° C./40 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was283.4 mg KOH/g and the solidification temperature was 5° C.

Example 9

1.6 wt % of isostearic acid was added to the amine compound synthesizedin Example 3, and the mixture was stirred at 60° C. for 30 minutes. Thisblended product had a solidification temperature of 10° C.

Example 10

2.5 wt % of 2-ethylhexanoic acid was added to the amine compoundsynthesized in Example 4, and the mixture was stirred at 60° C. for 30minutes. This blended product had a solidification temperature of 8° C.

Example 11

3.5 wt % of 2-ethylhexanoic acid was added to the amine compoundsynthesized in Example 6, and the mixture was stirred at 60° C. for 30minutes. This blended product had a solidification temperature of 6° C.

Example 12

200 g of tallow alkylmonoamine (total amine value: 214 mg KOH/g) wasweighed to feed into a 1 liter four neck flask and heated to 65° C. 92.6g of paraformaldehyde was charged dividing almost equally into fourportions, and after completing charging, the reaction was continued at65° C. for 2 hours. Dehydration was carried out with the final conditionof 75° C./50 mm Hg to obtain a reaction product having a total aminevalue of 178 mg KOH/g and a solidification temperature of 10° C.

Example 13

360 g of tallow alkylpropylenediamine (total amine value: 342 mg KOH/g)was weighed to feed into a 1 liter four neck flask and heated to 65° C.128 g of acetone was dropwise added over a period of one hour, and themixture was aged at 65° C. for 2 hours. Dehydration was carried out withthe final condition of 75° C./50 mm Hg to obtain a reaction producthaving a total amine value of 322 mg KOH/g and a solidificationtemperature of 4° C.

Example 14

250 g of tallow alkylpropylenediamine (total amine value: 342 mg KOH/g)was weighed to feed into a 1 liter four neck flask and heated to 95° C.66 g of methyl ethyl ketone was dropwise added over a period of onehour, and the solution was aged at 95° C. for 2 hours. Dehydration wascarried out in the final condition of 95° C./50 mm Hg to obtain areaction product having a total amine value of 330 mg KOH/g and asolidification temperature of 4° C.

The charged mole ratios of the raw material amines to the carbonylcompounds in Examples 1 to 14 are shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                                Mole                                                    Kind of raw material ratio                                                  ______________________________________                                        Ex. 1       Formaldehyde/tallow                                                                           2.0                                                  alkylpropylenediamine                                                        Ex. 2 Formaldehyde/tallow 2.0                                                  alkylpropylenediamine                                                        Ex. 3 Formaldehyde/tallow 1.0                                                  alkylpropylenediamine                                                        Ex. 4 Formaldehyde/tallow 1.5                                                  alkyldipropylenetriamine                                                     Ex. 5 Formaldehyde/tallow 2.5                                                  alkyltripropylenetetraamine                                                  Ex. 6 Formaldehyde/tallow 0.7                                                  alkyltripropylenetetraamine                                                  Ex. 7 Acetaldehyde/tallow 1.5                                                  alkyltripropylenetetraamine                                                  Ex. 8 n-Butylaldehyde/stearyl- 2.0                                             ethylenediamine                                                              Ex. 9 Formaldehyde/tallow 1.0                                                  alkylpropylenediamine                                                        Ex. 10 Formaldehyde/tallow 1.5                                                 alkylpropylenetriamine                                                       Ex. 11 Formaldehyde/tallow 0.7                                                 alkyltripropylenetetraamine                                                  Ex. 12 Paraformaldehyde/ 1.5                                                   tallow alkylmonoamine                                                        Ex. 13 Acetone/tallow 2.0                                                      alkylpropylenediamine                                                        Ex. 14 Methyl ethyl ketone/tallow 1.2                                          alkylpropylenediamine                                                      ______________________________________                                    

[Evaluation of Interface Activity]

Hydrochloride aqueous solutions of the amine compounds prepared inExamples 1 to 9 and 12 to 14 and various amines prepared in ComparativeExamples 1 to 4 shown below were prepared to determine interfacialtensions with oil. A pH of all solutions was adjusted as to be 3. Theoil used was prepared by blending straight asphalt (penetration: 80 to100) with gas oil No. 1 (JIS K 2204) in a weight ratio of 50/50. Theinterfacial tension was determined by a spinning drop method andcalculated by the following equation:

    γ=0.552Δρ×h.sup.3 /f.sup.2

γ: interfacial tension dyne/cm

Δρ: density difference g/cm³

h : width of oil droplet mm

f : rotation speed millisecond/rotation

The measuring results are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                                 Interfacial tension                                                    dyne/cm                                                                                40° C.*                                                                             60° C.*                                                                        80° C.*                                ______________________________________                                        Example 1  2.82         2.40    2.20                                            Example 2 2.92 2.50 2.30                                                      Example 3 2.10 1.80 1.50                                                      Example 4 2.50 2.30 2.10                                                      Example 5 2.92 2.42 2.26                                                      Example 6 2.03 1.70 1.42                                                      Example 7 2.02 1.90 1.65                                                      Example 8 2.40 2.15 1.95                                                      Example 9 2.84 2.41 2.22                                                      Example 12 3.09 2.85 2.65                                                     Example 13 2.56 2.40 2.30                                                     Example 14 2.76 2.58 2.42                                                     Comparative 6.25 5.30 4.90                                                    Example 1                                                                     Comparative 4.10 3.80 3.40                                                    Example 2                                                                     Comparative 3.50 3.20 2.90                                                    Example 3                                                                     Comparative 3.74 3.45 3.10                                                    Example 4                                                                   ______________________________________                                         *temperatures for measuring the interfacial tensions                          Note:                                                                         Comparative Example 1: tallow alkylaminopropylamineethylene oxide 10 mole     adduct                                                                        Comparative Example 2: 1stearoxy-2-aminopropoxyethylene                       Comparative Example 3: oleylaminopropylamine                                  Comparative Example 4: tallow alkyltripropylenetetraamineethylene oxide 4     moles adduct                                                             

It can be found that the compounds of the present invention provide lowinterfacial tensions and have excellent interface activities as comparedwith those of the comparative compounds.

[Evaluation as Asphalt Emulsifier]

The compound of the present invention can be used as a component for anasphalt emulsifier used for road paving, roofing and water-proofing forrevetment. Next, the examples thereof will be shown.

Aqueous solutions of the amine compounds prepared in Examples 1 to 14and various amines prepared in Comparative Examples 1 to 4 describedabove were prepared in the forms of hydrochlorides. 415 g of the aqueoussolution was heated to 50° C. and fed into a harrel type homogenizer atthe same time as 600 g of straight asphalt having a penetration of 60 to80, which had been molten by heating to 140° C., whereby an asphaltemulsion was produced. An addition amount of the surfactant was 0.3 wt %based on the sum of water and the asphalt. The emulsion was used todetermine an asphalt particle diameter, an evaporation residual content,a viscosity, a sieve residual content, and a storage stability. Thesetests were carried out in accordance with ASTM D244-86. The resultsthereof are shown in Table 7.

Details on methods for determining the asphalt particle diameter, theevaporation residual content, the viscosity, the sieve residual contentand the storage stability will be described below.

Measuring method for asphalt particle diameter:

Determined by a laser scattering particle analyzer (LA700, mfd. byHoriba Seisakusho Co. Ltd.).

Measuring method for evaporation residual content (%):

00±1 g of asphalt emulsion sample 3 was weighed into a prescribed vesseland heated on an electric heater for 20 to 30 minutes while stirring.The sample was further heated at 160° C. for one minute after it wasconfirmed that no water has been left. Then, the sample was left tostand for cooling down to room temperatures, and a residue (g) onevaporation was weighed. A percentage of the residue on evaporationbased on the sample was determined to obtain an evaporation residualcontent (%).

Measuring method for sieve residual content (%):

A 1.18 mm net sieve having a depth of about 20 mm and a diameter ofabout 75 mm and a pan (metallic or ceramic) having a diameter of about100 mm were precisely weighed by up to 0.5 g. The sieve is wetted indistilled water. 500±5 g of asphalt emulsion sample was weighed to feedinto a beaker and poured on the sieve. The sieve was sufficiently washedwith distilled water until an emulsion color of the residue on the sievehas been lost. Further, distilled water used for washing the beaker waspoured as well on the sieve. The sieve was placed on the pan and putinto a thermostatic bath of 110° C. to dry the sieve for 2 hours. Afterleaving to stand the sieve for cooling down to room temperatures, thewhole weight of the sieve is weighed. The sieve residual content (%) wascalculated by the following equation, and the value thus obtained wasrounded to the first decimal place. ##EQU1## R : sieve residual content(%) M1: weight (g) of the sample

M2: total weight (g) of sieve and pan

M3: total weight (g) of residue, sieve and pan

Evaluation Method for Storage Stability:

250 ml of asphalt emulsion produced was put into a prescribed cylinderand left for standing at a temperature of about 20° C. for 5 days. About50 g of each sample was taken out of drawing ports in upper and lowerparts of the cylinder to determine evaporation residual content (%). Thestorage stability was evaluated by a difference in the evaporationresidual contents in the upper and lower parts. The smaller thedifference is, the more stable and better the emulsion is.

Further, the amine compounds obtained in Examples 1, 3 and 7 were usedin combination with the other surfactants shown in Table 8 to similarlyevaluate them as the asphalt emulsifiers. The results thereof are shownin Table 8.

                                      TABLE 7                                     __________________________________________________________________________                 Evaporation                                                         Particle residual viscosity* Sieve Storage                                   Kind of diameter content (25° C.) residual stability                   emulsifier μm wt % Saybolt sec* content wt % 5 days Δ%             __________________________________________________________________________    Ex. 1  3.4   62.6   22     0.1    3.3                                           Ex. 2 3.6 61.6 20 0.0 3.9                                                     Ex. 3 2.8 61.0 22 0.1 2.0                                                     Ex. 4 2.9 63.5 24 0.0 2.2                                                     Ex. 5 4.2 62.3 22 0.2 4.0                                                     Ex. 6 3.7 62.2 22 0.1 3.5                                                     Ex. 7 3.5 62.9 23 0.0 2.1                                                     Ex. 8 4.0 62.8 22 0.1 4.1                                                     Ex. 9 3.2 61.9 21 0.1 3.0                                                     Ex. 10 3.1 62.0 22 0.1 2.2                                                    Ex. 11 3.5 61.5 22 0.1 2.9                                                    Ex. 12 4.5 62.1 20 0.2 3.9                                                    Ex. 13 3.8 61.8 21 0.2 3.4                                                    Ex. 14 3.6 62.5 20 0.1 3.1                                                    Comp. Ex. 1 5.8 62.0 19 0.8 8.6                                               Comp. Ex. 2 5.6 62.7 19 0.4 10.2                                              Comp. Ex. 3 7.4 63.4 18 1.6 16.1                                              Comp. Ex. 4 6.5 63.2 19 0.7 11.5                                              Comp. Ex. 5 6.8 63.1 22 0.5 12.3                                              Comp. Ex. 6 10.2 61.8 18 2.8 35.6                                           __________________________________________________________________________     *Value (flow time) determined by means of a Saybolt viscometer                Note:                                                                         Comparative Example 5: nonylphenolethylene oxide 20 moles adduct              Comparative Example 6: sodium stearylsulfate                             

                  TABLE 8                                                         ______________________________________                                                                       Sieve                                            Kind of  Evaporation residual Storage                                         emulsifier Other surfactant residual content stability                        (wt %) (wt %) content wt % wt % 5 days Δ%                             ______________________________________                                        Ex. 1  Ca lignosulfate                                                                             61.5      0.1    2.8                                       (0.25) (0.15)                                                                 Ex. 3 Stearylamine-ethylene 60.9 0.2 2.6                                      (0.25) oxide 4 moles adduct                                                    (0.10)                                                                       Ex. 3 Polyethylene glycol 61.5 0.1 1.8                                        (0.35) (0.08)                                                                  (molecular wt: 800)                                                          Ex. 7 Methyl cellulose 62.8 0.1 1.5                                           (0.20) (0.10)                                                                  (molecular wt:                                                                10,000)                                                                    ______________________________________                                    

It can be found from the test results shown above that the compounds ofthe present invention can provide cationic surfactants which areimproved in handling easiness that they are liquid at room temperatureswhile maintaining excellent emulsifying abilities.

Examples 15 to 21

200 g of hydrogenated tallow alkylpropylenediamine (total amine value:341 mg KOH/g) was weighed to feed into a 1 liter four neck flask andheated to 65° C. 65.6 g of isobutylaldehyde and organic acids of kindsand amounts shown in Table 9 were dropwise added over a period of 2hours. After aging at the same temperature for one hour, dehydration wascarried out. The final condition of the dehydration was 75° C./50 mm Hg.Then, the reaction mixture was cooled down to 60° C., and alcohols ofkinds and amounts shown in Table 9 were added to blend.

                  TABLE 9                                                         ______________________________________                                                          Addition           Addition                                    Kind of amount  amount                                                       Ex. organic acid (g) Kind of alcohol (g)                                    ______________________________________                                        15   No addition  0        No addition                                                                             0                                          16 2-Ethylhexanoic 12 No addition 0                                            acid                                                                         17 No addition 0 Polyethylene 4                                                  glycol (average                                                               molecular                                                                     weight:                                                                       200)                                                                       18 2-Ethylhexanoic 12 Polyethylene 4                                           acid  glycol (average                                                           molecular                                                                     weight:                                                                       200)                                                                       19 2-Ethylhexanoic 20 Glycerol 2                                               acid                                                                         20 Caprylic acid 10 Polyglycerol 12                                           21 Heptanoic acid 2 Polypropylene 30                                             glycol; triol                                                                 type (average                                                                 molecular                                                                     weight 300)                                                              ______________________________________                                    

Examples 22 to 28

200 g of hydrogenated tallow alkylpropylenediamine (total amine value:340 mg KOH/g) was weighed to feed into a 1 liter four neck flask andheated to 65° C. 98.3 g of 2-ethylhexylaldehyde was dropwise addedthereto over a period of 2 hours. After aging at the same temperaturefor one hour, dehydration was carried out. The final condition of thedehydration was 75° C./50 mm Hg. Then, the reaction mixture was cooleddown to 60° C., and organic acids and alcohols of kinds and amountsshown in Table 10 were added to blend.

                  TABLE 10                                                        ______________________________________                                                         Addition            Addition                                    Kind of amount  amount                                                       Ex. organic acid (g) kind of alcohol (g)                                    ______________________________________                                        22   2-Ethylhexanoic                                                                           12        No addition                                                                             0                                           acid                                                                         23 No addition 0 Glycerol 4                                                   24 2-Ethylhexanoic 30 Polyethylene 8                                           acid  glycol (average                                                           molecular weight                                                              400)                                                                       25 2-Ethylhexanoic 12 Glycerol 4                                               acid                                                                         26 Caproic acid 4 Polyglycerol 12                                             27 Pentanoic acid 8 Ethylene glycol 4                                         28 Isobutyric acid 2 Propylene glycol 20                                    ______________________________________                                    

[Evaluation as Asphalt Emulsifier]

The emulsifiers obtained in Examples 15 to 28 described above and theemulsifiers obtained in Comparative Examples 7 to 10 shown below weremeasured for solidification temperatures and presence of turbidity. Theresults thereof are shown in Table 11. The presence of turbidity wasdetermined in the following manner.

Measurement of the presence of turbidity

The presence of turbidity of the respective amines was determined byvisual observation after the storage (with naked eyes) at 15° C. for onemonth.

Next, aqueous solutions of the amine compounds obtained in Examples 15to 28 and various amines obtained in Comparative Examples 7 to 10described above were prepared in the forms of hydrochlorides. 415 g ofthe aqueous solution was heated to 50° C. and fed into a harrel typehomogenizer at the same time as 600 g of straight asphalt having apenetration of 60 to 80, which had been molten by heating to 140° C.,whereby an asphalt emulsion was produced. An addition amount of thesurfactant was 0.3 wt % based on the sum of water and the asphalt. Theemulsion was used to determine an asphalt particle diameter, anevaporation residual content, a viscosity, a sieve residual content, anda storage stability. These tests were carried out in accordance withASTM D244-86. The results thereof are shown in Table 11.

                                      TABLE 11                                    __________________________________________________________________________                            Evaporation                                              Solidification Presence Particle residual Viscosity Sieve residual                                                    Storage                              Kind of temperature of diameter content (25                                                                            ° C.) content stability       emulsifier (°C.) turbidity μm wt % Saybolt sec wt % 5 days                                                   Δ                            __________________________________________________________________________    Ex. 15 -6     Present                                                                            3.3  61.2  22    0.1    3.3                                  Ex. 16 -7 None 2.8 61.8 21 0.1 3.2                                            Ex. 17 -6 None 2.9 61.7 20 0.0 3.2                                            Ex. 18 -7 None 3.1 62.7 20 0.1 3.0                                            Ex. 19 -5 None 3.7 61.1 22 0.2 3.7                                            Ex. 20 -6 None 3.5 60.8 21 0.1 3.9                                            Ex. 21 -7 None 3.3 61.2 20 0.0 4.1                                            Ex. 22 3 None 3.9 62.2 22 0.1 2.2                                             Ex. 23 3 None 4.1 62.0 22 0.1 2.5                                             Ex. 24 2 None 3.9 61.8 23 0.2 4.6                                             Ex. 25 2 None 4.2 61.8 22 0.1 3.1                                             Ex. 26 2 None 3.8 61.7 20 0.1 3.8                                             Ex. 27 3 None 3.7 61.9 21 0.2 3.2                                             Ex. 28 1 None 3.8 62.1 21 0.1 3.8                                             Comp. Ex. 7 0 Present 5.8 62.0 19 0.8 8.6                                     Comp. Ex. 8 2 Present 5.6 62.7 19 0.4 10.2                                    Comp. Ex. 9 0 None 7.4 63.4 19 1.6 16.0                                       Comp. Ex. 10 15 None 6.5 63.2 19 0.7 11.5                                   __________________________________________________________________________     Comparative Example 7: tallow alkylaminopropylamineethylene oxide 10 mole     adduct                                                                        Comparative Example 8: 1stearoxy-2-aminopropoxyethylene                       Comparative Example 9: oleylaminopropylamine                                  Comparative Example 10: tallow alkyltripropylenetetraamineethylene oxide      moles adduct                                                             

[Evaluation of Emulsifying Ability by Difference in pH]

A similar experiment in which a pH of a hydrochloride aqueous solutionprepared using the amine compound obtained in Example 16 was varied wascarried out to evaluate an effect of pH exerted on a ability as anasphalt emulsifier. The results thereof are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                              Evaporation   Sieve      Storage                                           residual residual stability                                                  pH content (wt %) content (wt %) (5 days Δ%)                          ______________________________________                                        0.8   60.6          0.1        2.2                                              2.0 61.6 0.0 3.9                                                              3.2 60.9 0.3 4.4                                                              4.5 61.1 0.8 8.3                                                            ______________________________________                                    

It can be found from the test results shown above that the compounds ofthe present invention can provide emulsifiers for producing bituminousemulsions, which maintain excellent emulsifying abilities and are easyto handle and which are liquid at room temperatures.

Examples 29 to 64 and Comparative Examples 11 to 20

Synthetic compounds and comparative compounds shown below were used tocarry out the following examples and comparative examples.

Synthetic Compound 1

200 g of hydrogenated tallow alkylmonoamine (total amine value: 215 mgKOH/g) was weighed to feed into a 1 liter four neck flask and heated to65° C. 82.8 g of isobutylaldehyde was dropwise added over a period of 2hours. After aging at the same temperature for one hour, dehydration wascarried out. The final condition of the dehydration was 75° C./50 mm Hg.The resulting reaction product showed fluidity at room temperatures, andan analysis thereof resulted in showing that the total amine value was187 mg KOH/g and the solidification temperature was 15° C.

Synthetic Compound 2

200 g of hydrogenated tallow alkylmonoamine (total amine value: 215 mgKOH/g) was weighed to feed into a 1 liter four neck flask and heated to80° C. 141.0 g of lauraldehyde was dropwise added over a period of 2hours. After aging at 85° C. for one hour, dehydration was carried out.The final condition of the dehydration was 85° C./30 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 126mg KOH/g and the solidification temperature was 9° C.

Synthetic Compound 3

141.0 g of tallow alkylpropylenediamine (total amine value: 341 mgKOH/g) 200 g was weighed to feed into a 1 liter four neck flask andheated to 65° C. 65.6 g of isobutylaldehyde was dropwise added over aperiod of 2 hours. After aging at the same temperature for one hour,dehydration was carried out. The final condition of the dehydration was75° C./50 mm Hg. The resulting reaction product showed fluidity at roomtemperatures, and an analysis thereof resulted in showing that the totalamine value was 288 mg KOH/g and the solidification temperature was -6°C.

Synthetic Compound 4

200 g of tallow alkyldipropylenetriamine (total amine value: 438 mgKOH/g) was weighed to feed into a 1 liter four neck flask and heated to65° C. 56.2 g of isobutylaldehyde was dropwise added over a period of 2hours. After aging at the same temperature for one hour, dehydration wascarried out. The final condition of the dehydration was 75° C./50 mm Hg.The resulting reaction product showed fluidity at room temperatures, andan analysis thereof resulted in showing that the total amine value was358 mg KOH/g and the solidification temperature was -6° C.

Synthetic Compound 5

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 65° C.(total amine value: 323 mg KOH/g). 98.3 g of 37% formalin aqueoussolution was dropwise added thereto over a period of 2 hours. Afteraging at the same temperature for one hour, dehydration was carried out.The final condition of the dehydration was 75° C./50 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 196mg KOH/g and the solidification temperature was 8° C.

Synthetic Compound 6

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 65° C.(total amine value: 323 mg KOH/g). 59.2 g of 90% acetaldehyde aqueoussolution was dropwise added thereto over a period of 2 hours. Afteraging at the same temperature for one hour, dehydration was carried out.The final condition of the dehydration was 75° C./50 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 262mg KOH/g and the solidification temperature was 15° C.

Synthetic Compound 7

60 g of hydrogenated tallow alkylmonoamine, 100 g of hydrogenated tallowalkylpropylenediamine and 40 g of hydrogenated tallowalkyldipropylenetriamine were weighed to feed into a 1 liter four neckflask and heated to 65° C. (total amine value: 318 mg KOH/g). 69.3 g ofpropionaldehyde was dropwise added over a period of 2 hours. After agingat the same temperature for one hour, dehydration was carried out. Thefinal condition of the dehydration was 75° C./50 mm Hg. The resultingreaction product showed fluidity at room temperatures, and an analysisthereof resulted in showing that the total amine value was 255 mg KOH/gand the solidification temperature was 15° C.

Synthetic Compound 8

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 65° C.(total amine value: 323 mg KOH/g). 65.4 g of butylaldehyde was dropwiseadded over a period of 2 hours. After aging at the same temperature forone hour, dehydration was carried out. The final condition of thedehydration was 75° C./50 mm Hg. The resulting reaction product showedfluidity at room temperatures, and an analysis thereof resulted inshowing that the total amine value was 250 mg KOH/g and thesolidification temperature was 6° C.

Synthetic Compound 9

60 g of hydrogenated tallow alkylmonoamine, 100 g of hydrogenated tallowalkylpropylenediamine and 40 g of hydrogenated tallowalkyldipropylenetriamine were weighed to feed into a 1 liter four neckflask and heated to 65° C. (total amine value: 318 mg KOH/g). 64.5 g ofisobutylaldehyde was dropwise added over a period of 2 hours. Afteraging at the same temperature for one hour, dehydration was carried out.The final condition of the dehydration was 75° C./50 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 267mg KOH/g and the solidification temperature was 10° C.

Synthetic Compound 10

60 g of hydrogenated tallow alkylmonoamine, 100 g of hydrogenated tallowalkylpropylenediamine and 40 g of hardened tallowalkyldipropylenetriamine were weighed to feed into a 1 liter four neckflask and heated to 85° C. (total amine value: 318 mg KOH/g). 95.0 g ofbenzaldehyde was dropwise added over a period of 2 hours. After aging atthe same temperature for one hour, dehydration was carried out. Thefinal condition of the dehydration was 85° C./50 mm Hg. The resultingreaction product showed fluidity at room temperatures, and an analysisthereof resulted in showing that the total amine value was 260 mg KOH/gand the solidification temperature was 5° C.

Synthetic Compound 11

60 g of hydrogenated tallow alkylmonoamine, 100 g of hydrogenated tallowalkylpropylenediamine and 40 g of hydrogenated tallowalkyldipropylenetriamine were weighed into a 1 liter four neck flask andheated to 85C (total amine value: 318 mg KOH/g). 61.2 g of2-ethylhexylaldehyde was dropwise added over a period of 2 hours. Afteraging at the same temperature for one hour, dehydration was carried out.The final condition of the dehydration was 85° C./40 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 236mg KOH/g and the solidification temperature was 4° C.

Synthetic Compound 12

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 65° C.(total amine value: 323 mg KOH/g). 111.6 g of lauraldehyde was dropwiseadded over a period of 2 hours. After aging at 80° C. for one hour,dehydration was carried out. The final condition of the dehydration was85° C./30 mm Hg. The resulting reaction product showed fluidity at roomtemperatures, and an analysis thereof resulted in showing that the totalamine value was 210 mg KOH/g and the solidification temperature was -3°C.

Synthetic Compound 13

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 65° C.(total amine value: 323 mg KOH/g). 116.4 g of palmitaldehyde wasdropwise added over a period of 2 hours. After aging at 80° C. for onehour, dehydration was carried out. The final condition of thedehydration was 85° C./30 mm Hg. The resulting reaction product showedfluidity at room temperatures, and an analysis thereof resulted inshowing that the total amine value was 208 mg KOH/g and thesolidification temperature was 5° C.

Synthetic Compound 14

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 60° C.(total amine value: 323 mg KOH/g). 70.3 g of acetone was dropwise addedover a period of 2 hours. After aging at the same temperature for onehour, dehydration was carried out. The final condition of thedehydration was 75° C./30 mm Hg. The resulting reaction product showedfluidity at room temperatures, and an analysis thereof resulted inshowing that the total amine value was 265 mg KOH/g and thesolidification temperature was 12° C.

Synthetic Compound 15

60 g of hydrogenated tallow alkylmonoamine, 100 g of hydrogenated tallowalkylpropylenediamine and 40 g of hydrogenated tallowalkyldipropylenetriamine were weighed to feed into a 1 liter four neckflask and heated to 60° C. (total amine value: 318 mg KOH/g). A mixtureof 34.7 g of propionaldehyde and 43.0 g of isobutylaldedhyde wasdropwise added over a period of 2 hours. After aging at the sametemperature for one hour, dehydration was-carried out. The finalcondition of the dehydration was 75° C./50 mm Hg. The resulting reactionproduct showed fluidity at room temperatures, and an analysis thereofresulted in showing that the total amine value was 256 mg KOH/g and thesolidification temperature was 12° C.

Synthetic Compound 16

60 g of stearylmonoamine, 100 g of stearylpropylenediamine and tallow 40g of alkyltripropylenetetraamine were weighed to feed into a 1 literfour neck flask and heated to 65° C. (total amine value: 329 mg KOH/g).66.4 g of isobutylaldehyde was dropwise added over a period of 2 hours.After aging at the same temperature for 2 hours, dehydration was carriedout. The final condition of the dehydration was 80° C./40 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 274mg KOH/g and the solidification temperature was 9° C.

Synthetic Compound 17

60 g of hydrogenated tallow alkylmonoamine, 100 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine areweighed to feed into a 1 liter four neck flask and heated to 85° C.(total amine value: 323 mg KOH/g). 65.5 g of isobutylaldehyde wasdropwise added over a period of 2 hours. After aging at the sametemperature for one hour, dehydration was carried out. The finalcondition of the dehydration was 85° C./40 mm Hg. The resulting reactionproduct showed fluidity at room temperatures, and an analysis thereofresulted in showing that the total amine value was 267 mg KOH/g and thesolidification temperature was 5° C.

Synthetic Compound 18

100 g of hydrogenated tallow alkylmonoamine, 80 g of tallowalkylpropylenediamine and 20 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 80° C.(total amine value: 288 mg KOH/g). 69.4 g of isobutylaldehyde wasdropwise added over a period of 2 hours. After aging at the sametemperature for one hour, dehydration was carried out. The finalcondition of the dehydration was 85° C./40 mm Hg. The resulting reactionproduct showed fluidity at room temperatures, and an analysis thereofresulted in showing that the total amine value was 240 mg KOH/g and thesolidification temperature was 8° C.

Synthetic Compound 19

40 g of hydrogenated tallow alkylmonoamine, 120 g of tallowalkylpropylenediamine and 40 g of tallow alkyldipropylenetriamine wereweighed to feed into a 1 liter four neck flask and heated to 75° C.(total amine value: 335 mg KOH/g). 64.6 g of isobutylaldehyde wasdropwise added over a period of 2 hours. After aging at the sametemperature for one hour, dehydration was carried out. The finalcondition of the dehydration was 85° C./40 mm Hg. The resulting reactionproduct showed fluidity at room temperatures, and an analysis thereofresulted in showing that the total amine value was 280 mg KOH/g and thesolidification temperature was 5° C.

Synthetic Compound 20

60 g of hydrogenated tallow alkylmonoamine and 140 g of tallowalkylpropylenediamine were weighed to feed into a 1 liter four neckflask and heated to 75° C. (total amine value: 303 mg KOH/g). 55.0 g ofisobutylaldehyde was dropwise added over a period of 2 hours. Afteraging at the same temperature for one hour, dehydration was carried out.The final condition of the dehydration was 85° C./40 mm Hg. Theresulting reaction product showed fluidity at room temperatures, and ananalysis thereof resulted in showing that the total amine value was 258mg KOH/g and the solidification temperature was 3° C.

Synthetic Compound 21

5.0 wt % of 2-ethylhexanoic acid and 1.5 wt % of PEG 200 based on theamine compound obtained in Synthetic Compound 17 were added the aminecompound, and the components were mixed while stirring at 60° C. for 30minutes. This mixture had a solidification temperature of 4° C.

Synthetic Compound 22

1.5 wt % of linoleic acid and 3.0 wt % of PEG 200 of based on the aminecompound obtained in Synthetic Compound 17 were added to the aminecompound, and the components were mixed while stirring at 60° C. for 30minutes. This mixture had a solidification temperature of 5° C.

The raw material amines, aldehydes and the charge mole ratios are shownin Table 13. A ratio of the raw material amines is a weight ratio.

                  TABLE 13                                                        ______________________________________                                        Synthetic                         Mole                                          Compound Kind of raw material ratio                                         ______________________________________                                        1       Isobutylaldehyde/hydrogenated tallow                                                                    1.5                                            monoamine                                                                    2 Lauraldehyde/hydrogenated tallow monoamine 1.0                              3 Isobutylaldehyde/tallow diamine 1.5                                         4 Isobutylaldehyde/tallow triamine 1.5                                        5 Formaldehyde/hydrogenated tallow 2.0                                         monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             6 Acetaldehyde/hydrogenated tallow 2.0                                         monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             7 Propionaldehyde/hydrogenated tallow 2.0                                      monoamine:hydrogenated tallow diamine:                                        hydrogenated tallow triamine = 3:5:2                                         8 Butylaldehyde/hydrogenated tallow 1.5                                        monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             9 Isobutylaldehyde/hydrogenated tallow 1.5                                     monoamine:hydrogenated tallow diamine:                                        hydrogenated tallow triamine = 3:5:2                                         10 Benzaldehyde/hydrogenated tallow 1.5                                        monoamine:hydrogenated tallow diamine:                                        hydrogenated tallow triamine = 3:5:2                                         11 2-Ethylhexyaldehyde/hydrogenated tallow 0.8                                 monoamine:hydrogenated tallow diamine:                                        hydrogenated tallow triamine = 3:5:2                                         12 Lauraldehyde/hydrogenated tallow 1.0                                        monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             13 Palmitaldehyde/hydrogenated tallow 0.8                                      monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             14 Acetone/hydrogenated tallow monoamine 2.0                                   tallow diamine:tallow triamine = 3:5:2                                       15 Propionaldehyde (1.0 mole) + isobutyl- 2.0                                  aldehyde (1.0 mole)/hydrogenated tallow                                       monoamine:hydrogenated tallow                                                 diamine:hydrogenated tallow triamine =                                        3:5:2                                                                        16 Isobutylaldehyde/stearylmonoamine 1.5                                       steatyldiamine:tallow tetraamine =                                            3:5:2                                                                        17 Isobutylaldehyde/hydrogenated tallow 1.5                                    monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             18 Isobutylaldehyde/hydrogenated tallow 1.5                                    monoamine:tallow diamine:tallow                                               triamine = 5:4:1                                                             19 Isobutylaldehyde/hydrogenated tallow 1.5                                    monoamine:tallow diamine:tallow                                               triamine = 2:6:2                                                             20 Isobutylaldehyde/hydrogenated tallow 1.2                                    monoamine:tallow diamine = 3:7                                               21 Isobutylaldehyde/hydrogenated 1.5                                           monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                             22 Isobutylaldehyde/hydrogenated 1.5                                           monoamine:tallow diamine:tallow                                               triamine = 3:5:2                                                           ______________________________________                                    

[Evaluation as Asphalt Emulsifier]

The compound of the present invention can be used as a component for anasphalt emulsifier used for road paving, roofing and water-proofing forrevetment. Next, the examples thereof shall be shown.

Aqueous solutions of the amine compounds prepared in Synthetic Compounds1 to 22 and various amines prepared in Comparative Compounds 1 to 4 wereprepared in the forms of hydrochlorides. 415 g of the aqueous solutionwas heated to 50° C. and fed into a harrel type homogenizer at the sametime as 600 g of straight asphalt having a penetration of 60 to 80,which had been molten by heating to 140° C., whereby an asphalt emulsionwas produced. An addition amount of the surfactant was 0.25 wt % basedon the sum of water and the asphalt. The emulsion was used to determinean asphalt particle diameter, a storage stability and a viscosity. Thesetests were carried out in accordance with ASTM D244-86. The resultsthereof are shown in Tables 14 and 15.

                                      TABLE 14                                    __________________________________________________________________________                              Evaporation                                            Particle residual Viscosity Storage                                           diameter content [25° C.] stability                                   Kind of emulsifier (μm) (wt %) (Saybolt sec*) (5 days, Δ%)         __________________________________________________________________________    Ex. 29 Synthetic Compound 1/                                                                       3.0  60.2  31     2.5                                       Synthetic Compound 3 = 3/7                                                   Ex. 30 Synthetic Compound 2/ 3.2 60.8 30 2.8                                   Synthetic Compound 3 = 3/7                                                   Ex. 31 Synthetic Compound 2/ 4.0 60.9 26 3.5                                   Comparative Compound 1 = 3/7                                                 Ex. 32 Synthetic Compound 2/ 3.8 61.2 28 3.3                                   Comparative Compound 2 = 3/7                                                 Ex. 33 Synthetic Compound 2/ 3.4 60.5 29 3.0                                   Comparative Compound 3 = 3/7                                                 Ex. 34 Synthetic Compound 1/ 2.9 61.2 33 2.1                                   Synthetic Compound 3/                                                         Synthetic Compound 4 = 3/5/2                                                 Ex. 35 Synthetic Compound 5 4.8 61.5 22 4.2                                   Ex. 36 Synthetic Compound 6 3.1 60.5 33 2.4                                   Ex. 37 Synthetic Compound 7 3.6 61.1 36 0.8                                   Ex. 38 Synthetic Compound 8 3.2 60.7 31 2.3                                   Ex. 39 Synthetic Compound 9 2.8 60.8 38 0.6                                   Ex. 40 Synthetic Compound 10 3.0 61.0 65 1.0                                  Ex. 41 Synthetic Compound 11 3.4 60.9 33 1.0                                  Ex. 42 Synthetic Compound 12 3.9 60.6 27 3.9                                  Ex. 43 Synthetic Compound 13 4.2 60.4 26 4.1                                  Ex. 44 Synthetic Compound 14 3.3 61.3 32 2.6                                  Ex. 45 Synthetic Compound 15 3.4 60.8 38 0.8                                  Ex. 46 Synthetic Compound 16 3.0 61.2 30 1.2                                  Ex. 47 Synthetic Compound 17 2.7 61.0 27 2.4                                  Ex. 48 Synthetic Compound 18 5.1 61.5 35 2.0                                  Ex. 49 Synthetic Compound 19 2.5 60.9 23 2.6                                  Ex. 50 Synthetic Compound 20 2.9 61.9 32 2.2                                  Ex. 51 Synthetic Compound 21 2.8 61.3 26 2.6                                  Ex. 52 Synthetic Compound 22 2.8 60.8 27 2.5                                  Ex. 53 Synthetic Compound 3 5.4 61.2 18 8.3                                   Comp. Ex. 11 Comparative Compound 1 8.5 60.9 11 25.3                          Comp. Ex. 12 Comparative Compound 2 7.8 61.4 13 19.7                          Comp. Ex. 13 Comparative Compound 3 7.6 61.0 13 18.7                          Comp. Ex. 14 Comparative Compound 4 8.0 62.0 12 20.2                        __________________________________________________________________________     *Value (flow time) determined by means of a Saybolt viscometer                Comparative Example 1: tallow alkylaminopropylamineethylene oxide 10 mole     adduct                                                                        Comparative Example 2: 1stearoxy-2-aminopropoxyethylene                       Comparative Example 3: oleylaminopropylamine                                  Comparative Example 4: tallow alkyltripropylenetetraamineethylene oxide 4     moles adduct                                                             

Further, the addition amounts of the amine compounds obtained inSynthetic Compounds 9 and 17 and Comparative Compounds 1 and 2 werevaried to evaluate them as the asphalt emulsions. The results thereofare shown in Table 16.

                                      TABLE 16                                    __________________________________________________________________________               Addition                                                              amount of Particle Evaporation viscosity Sieve Storage                       Kind of emulsifier diameter residual [25° C.] residual stability       emulsifier % μm content wt % Saybolt sec content wt % 5 days,                                                   Δ%                               __________________________________________________________________________    Ex. 54                                                                            Synthetic                                                                            0.25 2.8  60.8  38    0.0   0.6                                       Compound 9                                                                   Ex. 55 Synthetic 0.20 4.5 60.2 27 0.0 0.8                                      Compound 9                                                                   Ex. 56 Synthetic 0.15 5.8 61.4 23 0.0 1.9                                      Compound 9                                                                   Ex. 57 Synthetic 0.125 6.8 61.1 19 0.0 3.8                                     Compound 9                                                                   Ex. 58 Synthetic 0.25 2.7 61.0 27 0.0 2.4                                      Compound 17                                                                  Ex. 59 Synthetic 0.20 3.7 60.8 21 0.0 2.6                                      Compound 17                                                                  Ex. 60 Synthetic 0.15 5.1 61.2 19 0.0 2.9                                      Compound 17                                                                  Comp. Comparative 0.35 4.8 61.5 19 0.3 4.2                                    Ex. 15 Compound 1                                                             Comp. Comparative 0.30 6.2 62.0 16 0.5 9.6                                    Ex. 16 Compound 1                                                             Comp. Comparative 0.25 8.5 60.9 11 1.0 25.3                                   Ex. 17 Compound 1                                                             Comp. Comparative 0.35 4.8 61.5 22 0.0 3.9                                    Ex. 18 Compound 2                                                             Comp. Comparative 0.30 5.8 60.9 19 0.1 8.6                                    Ex. 19 Compound 2                                                             Comp. Comparative 0.25 7.8 61.4 13 0.2 19.7                                   Ex. 20 Compound 2                                                           __________________________________________________________________________

The amine compounds obtained in Synthetic Compounds 7, 9 and 17 wereused in combination with the other surfactants shown in Table 17 toevaluate them as asphalt emulsifiers. The results thereof are shown inTable 17.

                                      TABLE 17                                    __________________________________________________________________________    Kind of              Evaporation                                                                          Sieve  Storage                                      emulsifier Other surfactant residual residual stability                       (wt %) (wt %) content (wt %) content (wt %) (5 days, Δ%)              __________________________________________________________________________    Ex. 61                                                                            Synthetic                                                                            Polycarboxylic acid                                                                     61.5   0.0    0.5                                           compound 7 (0.15)                                                             (0.25) [molecular wt:                                                          250,000]                                                                    Ex. 62 Synthetic Stearylamine- 60.9 0.0 0.6                                    compound 9 ethylene oxide 4 moles                                             (0.20) adduct (0.10)                                                         Ex. 63 Synthetic Methyl cellulose 62.8 0.0 0.3                                 compound 9 (0.10) [molecular                                                  (0.15) wt: 10,900]                                                           Ex. 64 Synthetic Polyalkylene glycol 61.5 0.0 1.8                              compound 17 distearyl ester                                                   (0.20) (0.05)                                                                  [molecular wt:                                                                20,000]                                                                   __________________________________________________________________________

It can be found from the test results described above that the compoundsof the present invention show emulsifying powers which are moreexcellent by twice or more than those of conventional liquid amineswhile maintaining liquidity at room temperatures.

BRIEF DESCRIPTION OF THE DRAWINGS

[FIG. 1]

A diagram showing the infrared absorption spectra of the tallowalkylpropylenediamine used as a raw material diamine and the resultingreaction product in Example 1.

[FIG. 2]

A diagram showing the H-NMR spectra of the tallow alkylpropylenediamineused as a raw material diamine used and the resulting reaction productin Example 1.

[FIG. 3]

A diagram showing the analytical results of the reaction productobtained in Example 1 by means of GPC.

[FIG. 4]

A diagram showing the analytical results of the reaction productobtained in Example 3 by means of GPC.

We claim:
 1. A method for emulsifying bitumens in water, comprisingmixing bitumens and water in the presence of an acid and a liquid aminecompound, wherein the liquid amine compound is prepared by reacting analiphatic amine having at least one hydrocarbon group having not lessthan 8 carbon atoms with a carbonyl compound; and feeding the mixtureand molten asphalt into an emulsifying apparatus wherein the emulsionobtained has a pH value of not more than
 5. 2. The method of claim 1,wherein the aliphatic amine is at least one selected from the groupconsisting of an aliphatic mono-amine and an aliphatic poly-amine. 3.The method of claim 1, wherein the aliphatic amine is a tallow amine ora hydrogenated tallow amine.
 4. The method of claim 1, wherein thealiphatic amine is an aliphatic mono-amine.
 5. The method of claim 1,wherein the aliphatic amine is an aliphatic poly-amine.
 6. The method ofclaim 1, wherein the aliphatic amine is a mixture of an aliphaticmono-amine and an aliphatic poly-amine.
 7. The method of claim 1,wherein the aliphatic amine is selected from the group consisting of atallow mono-amine, a tallow poly-amine, a hydrogenated tallow mono-amineand a hydrogenated tallow poly-amine.
 8. The method of claim 1, whereinthe carbonyl compound is an aldehyde having 1 to 18 carbon atoms.
 9. Themethod of claim 1, wherein the carbonyl compound is an aliphaticaldehyde or a heterocyclic aldehyde, both having 1 to 10 carbon atoms.10. The method of claim 1, wherein the carbonyl compound is a ketonehaving 3 to 8 carbon atoms.
 11. A method according to claim 1, whereinthe mixture comprises 50 to 80 wt % of bitumen, 50 to 20 wt % of water,and 0.05 to 10.0 wt % of the liquid amine compound.
 12. The method asclaimed in claim 11, further comprising adding to the mixture at leastone compound selected from the group consisting of (a) organic acids,(b) alcohols and (c) phenols.
 13. The method of claim 1, wherein thebitumens, water, the liquid amine compound and the acid are mixedtogether simultaneously.
 14. The method of claim 1, wherein the water,the liquid amine compound, and the acid are mixed together, and then theresulting aqueous solution is mixed with the bitumens to be emulsified.15. The method of claim 1, wherein the water, the liquid amine compound,and the acid are mixed together to form an acid salt of the liquidamine, and then the resulting aqueous solution is mixed with thebitumens to be emulsified.
 16. The method of claim 1, wherein thealiphatic amine has at least one hydrocarbon group having 8 to 22 carbonatoms.
 17. The method of claim 1, which further comprises mixing atleast one compound selected from the group consisting of (a) organicacids, (b) alcohols and (c) phenols.
 18. A process for producing anemulsifier by adding an acid to a liquid amine compound prepared byreacting an aliphatic amine having at least one hydrocarbon group having8 to 22 carbon atoms with a carbonyl compound to adjust the pH of anaqueous solution so as to be not more than
 5. 19. The process as claimedin claim 18, in which at least one compound selected from the groupconsisting of (a) organic acids, (b) alcohols and (c) phenols is furtheradded to the liquid amine compound.